molecular design of organic electrode active materials for...
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Molecular Design of Organic Electrode Active Materials for Aqueous
Rechargeable Magnesium-ion Battery
Masato Ito(Kyushu Univ.)
Sep. 22, 2015@PWTC, Kuala Lumpur
ISOC14
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Toward Large-Scale Electricity Storage
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Commercial Rechargeable Batteries using s-Block Element
Nickel-Metal hydride(NiMH)
Lithium-ion (LiB)
Sodium-sulfur(NaS)
AdvantageHigh power density High energy density Rare-metal free
Disadvantage •memory effect •Flammable•Less conductive•High cost
•High operation temp.•Corrosion of insulator•Dendritic-Na growth
Electrolyte Aqueous(KOH aq.)
Non-aqueous (Organic carbonate)
Solid(β-Al2O3)
Application Hybrid Vehicle Electric Vehicle Power Plant
Accident example Nothing •PC smoking and fire•Boeing 787 (2013)
•Toko-Takaoka (2011)•TEPCO (2013)
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O2 generation (E = 1.23 – 0.059pH)
H2 generation (E = – 0.059pH)
Stable Electrochemical Window
E (V) vs. NHE
‐1.5
‐1.0
‐0.5
0.0
0.5
1.0
1.5
14121086420pH
Stability Window of H2O
Clarke Number
ionic radius,Å (CN6)
standard electrode potential,
V (vs. SHE)
theoretical specific volume
capacity, Ah/cc
3Li 0.006 0.76 -3.045 2.05
11Na 2.63 1.02 -2.714 1.13
12Mg 1.93 0.72 -2.356 3.83
13Al 7.56 0.54 -1.676 8.05
Energy Density = Voltage x Capacity
Characteristics of Selected Ions
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Aqueous Rechargeable Battery: Historical Background
electrolyte cathode anode capacity(mAh/g) group (year)
5 M LiNO3 aq. LiMn2O4 VO2 10 Dahn (1994)sat. LiNO3 aq. LiCoO2 LiV3O8 55 Wu (2007)1 M Mg(NO3)2 aq. LiMn2O4 Pt 42 Munichandraiah (2008)1 M Li2SO4 aq. LiFePO4 LiTi2(PO4)3 82 Okada (2008)1 M Na2SO4 aq. Na0.44MnO2 AC 45 Whitacre (2010)2 M Na2SO4 aq. Zn NaTi2(PO4)3 121 Okada (2011)2 M Na2SO4 aq. Na0.44MnO2 NaTi2(PO4)3 42 Okada (2011)5 M LiNO3 aq. LiCoO2 DANTCBI 71 Zhan (2014)2 M MgSO4 aq. Zn DAAQ 260 This work (2014)
NN
O
O
O
On
DANTCBI
O
N
O
N
1,4-DAAQ
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reduction oxidation
Chem. Rev. 1992, 92, 1227Acta Cryst. E, 2005, 61, o1393
OHOH
OHOHHO
HOHOHO
HOHO OH
OH
O
O
O
O
O
O
8 H2O 2 H2O
Molecular Design of New Electrode Active Materials
X
X X
X
XX
X
X X
X
XX
X
X X
X
XX
X
X X
X
XX
2e-
2e-
2e-
2e-
2e-
2e-
X = CR2. NR, O
■Hexagonal Radialenes : 6-electron redox reaction at maximum
■The parent C6O6 molecule can not exist without hydration
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O
O
N
N
O
O
O
N
N
N
O
N
N
N
N
N
O
O
N
N
N
N
N
N
X6 = O4N2 X6 = O2N4 X6 = N6
O
O
O
O
X6 = O2C4
O
N
N
O
N
N
O
O
X6 = O2N2C2
Hetero[6]radialenesNew Candidates for Electrode Active Materials
The two contiguous exocyclic double bonds in C6O6 are replaced
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Experimental Setup and Conditions
CEWE
Ni wire
Ni mesh
RE
Zn foil
Zn wire
WE composite hetero[6]radialene:AB:PTFE = 70:25:5 (by weight)
electrolyte 2 M MgSO4 aq.
CE Zn metal, 99.9% (Nilaco)
RE Ag/AgCl (BAS)
current density 0.2 mA/cm2 (constant)@25 ℃
potential range -0.8~+0.6 V
WE = working electrode, CE = counter electrode, RE = reference electrodeAB = acetylene black (Denki Kagaku), PTFE = poly(tetrafluoroethylene) (Daikin)
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Charge/Discharge Profiles:Diaza-anthraquinone
N
N
O
O
O
O
1,4-DAAQ
N
O
O
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
• flat voltage plateau• just above the lower limit• clean reversible reaction
• initial capacity decrease• significant loss of energy
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N
N
O
O
N N
O
O
Pyrazine-substructure
N
N
O
O
1,4-DAAQ
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
• flat voltage plateaus• initial capacity decrease
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para- vs ortho-Quinone
N
N
O
O
O
N
N
O
1,4-DAAQ
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
• unattractive potential • initial capacity decrease
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Benzene Juncture
N
N
O
O
The benzene ring possibly prevents 1,4-addition of water at the surface.
N
N
O
O
1,4-DAAQ
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
-1.0
-0.5
0.0
0.5
1.0
Vol
tage
(V) v
s. A
g/A
gCl
300250200150100500Capacity (mAh/g)
1st 2nd
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Structural Change on Electrolysis : ex-situ IR
-1.0
-0.5
0.0
0.5
1.0V
olta
ge (V
) vs.
Ag/
AgC
l
300250200150100500Capacity (mAh/g)
1st 2nd
①Initial②Mg insertion
③Mg extraction
Wavenumber [cm-1]1800
1800
1600
1600
1400
1400
1200
1200
1000
1000
②
③
①
N
N
O
O
e e
Mg2+
electrodeelectrolyte
260 mA/g: one Mg per one 1,4-DAAQ
1,4-DAAQ
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MgMnSiO4
Summary
N
N
O
O
O
N
N
O
1,4-DAAQ
■1,4-DAAQ as a promising electrode material for Mg ion battery■Capacity of 260 mAh/g is largest ever for an aqueous battery■Attractive potential for an anode material■Judicious arrangement of four consecutive exocyclic double bonds
O2 generation (E = 1.23 – 0.059pH)
H2 generation (E = – 0.059pH)
Stable electrochemical window of H2O
E (V) vs. NHE
‐1.5
‐1.0
‐0.5
0.0
0.5
1.0
1.5
14121086420pH
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Acknowledgement
Prof. S. Okada(Kyushu Univ.)K. Chihara(Tokyo Univ. of Science)K. Nakamoto (Kyushu Univ.)T. Ikeda (Kyushu Univ.)